CN105186043B - All solid state LiMn2O4‑Li4Ti5O12Battery and preparation method thereof - Google Patents
All solid state LiMn2O4‑Li4Ti5O12Battery and preparation method thereof Download PDFInfo
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- CN105186043B CN105186043B CN201510610676.7A CN201510610676A CN105186043B CN 105186043 B CN105186043 B CN 105186043B CN 201510610676 A CN201510610676 A CN 201510610676A CN 105186043 B CN105186043 B CN 105186043B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention discloses a kind of all solid state LiMn2O4‑Li4Ti5O12The preparation method of battery, comprises the following steps：By LiMn2O4, conductive agent, solid electrolyte, aluminium powder be well mixed, compressing tablet formation one anode preform；By Li4Ti5O12, conductive agent, solid electrolyte, aluminium powder be well mixed, compressing tablet formation one negative pole precast body；The two panels anode preform or negative pole precast body, which are positioned over current collector aluminum foil both sides and heated, to be made negative or positive electrode precast body and current collector aluminum foil bond together to form positive plate and negative plate respectively；A solid electrolyte layer is formed on the surface of positive plate or negative plate；Positive plate and negative plate are stacked alternately, solid electrolyte layer is held between the positive plate and negative plate, a battery precast body is formed after hot pressing；And the moisture in removal battery precast body, and aluminum plastic film sealing obtains all solid state LiMn2O4‑Li4Ti5O12Battery.The present invention also provides a kind of all solid state LiMn obtained by the above method2O4‑Li4Ti5O12Battery.
Description
Technical field
The present invention relates to a kind of all solid state LiMn2O4-Li4Ti5O12Battery and preparation method thereof.
Background technology
Used electrolyte includes volatile and incendive organic solvent to current lithium battery mostly.It is higher in order to manufacture
The battery of output voltage, more high-energy-density and more large scale, it is necessary to use the electrolyte containing a large amount of organic solvents.And in battery
Organic bath cause serious fire and electrolyte leakage to happen occasionally.Overcome these safety problems and produce reliability
Battery, most efficient method be exactly with non-ignitable solid electrolyte replace inflammable liquid electrolyte.Solid lithium battery with
Traditional liquid electrolyte battery is compared, except having in addition to higher energy, it is thus also avoided that the liquid electrolytic confrontation container such as soda acid
Corrosion, and have the advantages that without leakage, storage life length, be easy to miniaturization, and temperature in use scope is wide so that lithium battery
Application expand to the working environments of a variety of particular/special requirements such as electric automobile, energy storage, space flight, biology and human body, it will
Increasingly influence and change the life of people.
In summary, the exploitation for solid lithium battery are of great immediate significance.
The content of the invention
The present invention provides a kind of all solid state LiMn2O4-Li4Ti5O12The preparation method of battery, comprises the following steps：
By LiMn2O4, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed an anode preform；
By Li4Ti5O12, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed a negative pole precast body；
The two panels anode preform and negative pole precast body are respectively placed in into the hot pressing of current collector aluminum foil both sides to be formed respectively
Positive plate and negative plate；
A solid electrolyte layer is formed on an at least surface for positive plate or negative plate；
Positive plate and negative plate are stacked alternately, make solid electrolyte layer and the positive plate and negative plate formation interlayer knot
A battery precast body is formed after structure, hot pressing；And
The moisture in battery precast body is removed, and aluminum plastic film sealing obtains all solid state LiMn2O4-Li4Ti5O12Battery.
Further, LiMn in the anode preform2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10：
0.1~1.0：0.5~1.5：0.5~1.5.
Further, LiMn in the anode preform2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10：
0.3~0.7：0.8~1.2：0.8~1.2.
Further, Li in the negative pole precast body4Ti5O12, conductive agent, the mass ratio of solid electrolyte and aluminium powder be
10：0.1~1.0：0.5~1.5：0.5~1.5.
Further, Li in the negative pole precast body4Ti5O12, conductive agent, the mass ratio of solid electrolyte and aluminium powder be
10：0.3~0.7：0.8~1.2：0.8~1.2.
Further, the solid electrolyte layer is formed by magnetically controlled sputter method.
Further, the anode preform and negative pole precast body are heated into 660 DEG C ~ 680 DEG C makes aluminium powder melt difference
Form positive plate and negative plate.
The present invention also provides a kind of all solid state LiMn2O4-Li4Ti5O12Battery, including：
Positive plate, including mixed uniformly LiMn2O4, conductive agent, solid electrolyte and metallic aluminium, wherein, metallic aluminium glues
Tie in LiMn2O4, between conductive agent and solid electrolyte；
Negative plate, including mixed uniformly Li4Ti5O12, conductive agent, solid electrolyte and metallic aluminium, wherein, metallic aluminium
It is bonded in Li4Ti5O12, between conductive agent and solid electrolyte；
Interlayer is the solid electrolyte layer between the positive plate and negative plate.
Further, LiMn in the positive plate2O4, conductive agent, the mass ratio of solid electrolyte and metallic aluminium be 10：0.1
~1.0：0.5~1.5：0.5~1.5.
Further, Li in the negative plate4Ti5O12, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10：0.1
~1.0：0.5~1.5：0.5~1.5.
A kind of all solid state LiMn that the present invention is provided2O4-Li4Ti5O12Battery not only has outside higher-energy, passes through metal
Aluminium can also make above-mentioned battery have good cycle performance and security performance as positive plate and the binding agent of negative plate.This
Outside, preparation method of the invention, also simple with processing procedure, the features such as easily industrialization is quoted.
Brief description of the drawings
Fig. 1 prepares all solid state LiMn to be provided in an embodiment of the present invention2O4-Li4Ti5O12The flow chart of battery.
Fig. 2 is all solid state LiMn obtained by the present embodiment 12O4-Li4Ti5O12The loop test curve map of battery.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining the present invention, rather than limitation of the invention.It also should be noted that, in order to just
Part related to the present invention rather than entire infrastructure are illustrate only in description, accompanying drawing.
It refer to Fig. 1, a kind of all solid state LiMn2O4-Li4Ti5O12The preparation method of battery, comprises the following steps：
S1, by LiMn2O4, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed an anode preform；
S2, by Li4Ti5O12, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed a negative pole precast body；
S3, is placed on current collector aluminum foil both sides by the two panels anode preform and negative pole precast body and hot pressing is formed respectively
Positive plate and negative plate；
S4, a solid electrolyte layer is formed on an at least surface for positive plate or negative plate；
S5, positive plate and negative plate are stacked alternately, and solid electrolyte layer is located between the positive plate and negative plate,
A battery precast body is formed after hot pressing；And
S6, removes the moisture in battery precast body, and aluminum plastic film sealing obtains all solid state LiMn2O4-Li4Ti5O12Electricity
Pond.
In step sl, LiMn in the anode preform2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be
10：0.1~1.0：0.5~1.5：0.5~1.5；It is preferred that, LiMn in the anode preform2O4, conductive agent, solid electrolyte and
The mass ratio of aluminium powder is 10：0.3~0.7：0.8~1.2：0.8~1.2；It is furthermore preferred that LiMn in the anode preform2O4, it is conductive
The mass ratio of agent, solid electrolyte and aluminium powder is 10：0.4~0.6：0.9~1.1：0.9~1.1.Add in the anode preform
The purpose for entering aluminium powder is to be LiMn2O4, conductive agent solid electrolyte binding agent.The solid electrolyte can be lithium
Ion conductor, such as β-Al2O3、LiPON、Li2S-P2S5Glass, Li10GeP2S12, NASICON, LISICON, perovskite structure
Li3xLa1-3xTiO3(LLT, 0<x<0.16) the solid electrolytic plastidome such as.The conductive agent can be activated carbon, conductive black, carbon
Nanotube, graphene or other types of conductive additive.
In step s 2, Li in the negative pole precast body4Ti5O12, conductive agent, the mass ratio of solid electrolyte and aluminium powder be
10：0.1~1.0：0.5~1.5：0.5~1.5；It is preferred that, Li in the negative pole precast body4Ti5O12, conductive agent, solid electrolyte
Mass ratio with aluminium powder is 10：0.3~0.7：0.8~1.2：0.8~1.2；It is furthermore preferred that Li in the negative pole precast body4Ti5O12、
The mass ratio of conductive agent, solid electrolyte and aluminium powder is 10：0.4~0.6：0.9~1.1：0.9~1.1.It is extremely prefabricated in the negative pole
The purpose that aluminium powder is added in body is to be Li4Ti5O12, conductive agent solid electrolyte binding agent and improve whole pole piece
Electric conductivity.
In step s3, it is preferred that heated in vacuum or atmosphere of inert gases, so that anti-oxidation.In addition, institute
State the fusing point that heating-up temperature is more than or equal to aluminium powder, i.e. more than or equal to 660 DEG C.In order to not destroy solid electrolyte,
Li4Ti5O12And LiMn2O4Structure, the heating-up temperature be 660 DEG C ~ 680 DEG C.It is preferred that, the heating-up temperature is 660 DEG C
~670℃.It is furthermore preferred that the heating-up temperature is 660 DEG C ~ 665 DEG C.Because heating-up temperature is more than aluminium powder fusing point, therefore, positive pole is pre-
The aluminium powder of body processed can melt, so as to be bonded in LiMn2O4, conductive agent solid electrolyte between.It is appreciated that the negative pole is pre-
Aluminium powder in body processed can also melt, so as to be bonded in Li4Ti5O12, conductive agent solid electrolyte between.Further, it is described
Heat time is preferably 10 minutes to 60 minutes.Further, including one annealing the step of, the annealing temperature be 400 DEG C ~
600 DEG C, annealing time is 1 hour to 2 hours.It is demonstrated experimentally that by annealing more stable positive plate can be obtained and negative
Pole piece.It is furthermore preferred that the annealing temperature is 500 DEG C ~ 600 DEG C.
In step s 4, a solid electrolyte layer can be formed on an at least surface for the positive plate or negative plate.Institute
Stating solid electrolyte layer can be formed by magnetically controlled sputter method or other methods.The thickness of the solid electrolyte layer can root
According to being actually needed selection, generally 1 micron to 10 microns.It is preferred that, the thickness of the solid electrolyte layer is micro- to 5 for 2 microns
Rice.It is furthermore preferred that the thickness of the solid electrolyte layer is 2 microns to 4 microns, so as to significantly improve the discharge and recharge of battery
Performance.
In step s 5, the hot pressing temperature is 600 DEG C ~ 660 DEG C.
In step s 6, it can be removed by boulton process, heat drying method or other method in battery precast body
Moisture, and all solid state LiMn is obtained by aluminum plastic film sealing2O4-Li4Ti5O12Battery.
The present invention also provides a kind of all solid state LiMn2O4-Li4Ti5O12Battery, including：
Positive plate, including mixed uniformly LiMn2O4, conductive agent, solid electrolyte and metallic aluminium, wherein, metallic aluminium glues
Tie in LiMn2O4, between conductive agent and solid electrolyte；
Negative plate, including mixed uniformly Li4Ti5O12, conductive agent, solid electrolyte and metallic aluminium, wherein, metallic aluminium
It is bonded in Li4Ti5O12, between conductive agent and solid electrolyte；
Solid electrolyte layer described in interlayer between positive plate and negative plate；
First collector, is arranged at side of the positive plate away from the solid electrolyte layer；And
Second collector, is arranged at side of the negative plate away from the solid electrolyte layer.
LiMn in the positive plate2O4, conductive agent, the mass ratio of solid electrolyte and metallic aluminium be 10：0.1~1.0：0.5~
1.5：0.5~1.5.It is preferred that, LiMn in the positive plate2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10：0.3
~0.7：0.8~1.2：0.8~1.2；It is furthermore preferred that LiMn in the positive plate2O4, conductive agent, the matter of solid electrolyte and aluminium powder
Amount is than being 10：0.4~0.6：0.9~1.1：0.9~1.1.
Further, Li in the negative plate4Ti5O12, conductive agent, the mass ratio of solid electrolyte and metallic aluminium be 10：
0.1~1.0：0.5~1.5：0.5~1.5.It is preferred that, Li in the negative plate4Ti5O12, conductive agent, solid electrolyte and aluminium powder
Mass ratio is 10：0.3~0.7：0.8~1.2：0.8~1.2；It is furthermore preferred that Li in the negative plate4Ti5O12, conductive agent, solid
The mass ratio of electrolyte and aluminium powder is 10：0.4~0.6：0.9~1.1：0.9~1.1.First collector and the second collector are excellent
Aluminium foil is elected as, so as to form good contact with the positive plate and negative plate.
Embodiment 1：
Weigh 1gLiMn2O4, 0.05g conductive blacks, 0.1g aluminium powders, the Li of 0.1g perovskite structures3xLa1-3xTiO3Mixing
Uniformly, 660 DEG C of hot-pressing processings under an inert atmosphere after compressing tablet, form positive plate；Weigh 1gLi4Ti5O12, 0.05g conductive blacks,
The Li of 0.1g aluminium powders, 0.1g perovskite structures3xLa1-3xTiO3It is well mixed, 660 DEG C of heat treatment under an inert atmosphere after compressing tablet,
Form negative plate；In the Li for the perovskite structure that the surface sputtering thickness of positive plate is 2 microns3xLa1-3xTiO3Film, so
Negative pole is placed on positive plate afterwards and the suitable aluminium foil of size is put at the back side of both positive and negative polarity, both positive and negative polarity is caused under modest pressure
Bonded together with solid electrolyte, aluminium foil is bonded together into electrode pair with both positive and negative polarity；Go after moisture removal with plastic-aluminum combined
Film sealing obtains battery.Fig. 2 is refer to, battery capacity is undamped after 210 charge and discharge cycles.
Embodiment 2：
Substantially the same manner as Example 1, difference is to contain 0.15g aluminium in anode preform and negative pole precast body
Powder.By it is demonstrated experimentally that battery capacity is undamped after 200 charge and discharge cycles.
Embodiment 3：
Substantially the same manner as Example 1, difference is to contain 0.05g aluminium in anode preform and negative pole precast body
Powder.By it is demonstrated experimentally that battery capacity is undamped after 180 charge and discharge cycles.
Embodiment 4：
Substantially the same manner as Example 1, difference is that the heat treatment temperature of anode preform and negative pole precast body is
670℃.By it is demonstrated experimentally that battery capacity is undamped after 200 charge and discharge cycles.
Embodiment 5：
Substantially the same manner as Example 1, difference is that the heat treatment temperature of anode preform and negative pole precast body is
680℃.By it is demonstrated experimentally that battery capacity is undamped after 180 charge and discharge cycles.
Embodiment 6：
Substantially the same manner as Example 1, difference is to contain 0.15g calcium in anode preform and negative pole precast body
The Li of perovskite like structure3xLa1-3xTiO3.By it is demonstrated experimentally that battery capacity is undamped after 200 charge and discharge cycles.
Embodiment 7：
Substantially the same manner as Example 1, difference is to be led in anode preform and negative pole precast body containing 0.05g
Electric carbon black.By it is demonstrated experimentally that battery capacity is undamped after 200 charge and discharge cycles.
Note, above are only presently preferred embodiments of the present invention and institute's application technology principle.It will be appreciated by those skilled in the art that
The invention is not restricted to specific embodiment described here, can carry out for a person skilled in the art it is various it is obvious change,
Readjust and substitute without departing from protection scope of the present invention.Therefore, although the present invention is carried out by above example
It is described in further detail, but the present invention is not limited only to above example, without departing from the inventive concept, also
Other more Equivalent embodiments can be included, and the scope of the present invention is determined by scope of the appended claims.
Claims (7)
1. a kind of all solid state LiMn2O4-Li4Ti5O12The preparation method of battery, it is characterised in that comprise the following steps：
By LiMn2O4, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed an anode preform；
By Li4Ti5O12, conductive agent, solid electrolyte, aluminium powder be well mixed, hot pressing formed a negative pole precast body；
The anode preform and the heating of negative pole precast body are answered with current collector aluminum foil in vacuum or atmosphere of inert gases
Close and form positive plate and negative plate respectively, wherein, heating-up temperature is 660 DEG C~680 DEG C, and the heat time is 10~50min, heating
Made annealing treatment afterwards, annealing temperature is 400~600 DEG C, annealing time is 1~2h；
A solid electrolyte layer is formed on an at least surface for positive plate or negative plate；
Positive plate and negative plate are stacked alternately, solid electrolyte layer is held between the positive plate and negative plate, hot pressing
Form a battery precast body；And
The moisture in battery precast body is removed, and aluminum plastic film sealing obtains all solid state LiMn2O4-Li4Ti5O12Battery.
2. all solid state LiMn according to claim 12O4-Li4Ti5O12The preparation method of battery, it is characterised in that described
LiMn in anode preform2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10:0.1~1.0:0.5~1.5:0.5
~1.5.
3. all solid state LiMn according to claim 22O4-Li4Ti5O12The preparation method of battery, it is characterised in that described
LiMn in anode preform2O4, conductive agent, the mass ratio of solid electrolyte and aluminium powder be 10:0.3~0.7:0.8~1.2:0.8
~1.2.
4. all solid state LiMn according to claim 12O4-Li4Ti5O12The preparation method of battery, it is characterised in that described
Li in negative pole precast body4Ti5O12, the mass ratio of conductive agent, solid electrolyte and aluminium powder is 10:0.1~1.0:0.5~1.5:
0.5~1.5.
5. all solid state LiMn according to claim 42O4-Li4Ti5O12The preparation method of battery, it is characterised in that described
Li in negative pole precast body4Ti5O12, the mass ratio of conductive agent, solid electrolyte and aluminium powder is 10:0.3~0.7:0.8~1.2:
0.8~1.2.
6. all solid state LiMn according to claim 12O4-Li4Ti5O12The preparation method of battery, it is characterised in that described
Solid electrolyte layer is formed by magnetically controlled sputter method.
7. a kind of all solid state LiMn2O4-Li4Ti5O12Battery, it is characterised in that according to claim 1~6 any one
Preparation method is prepared.
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| CN105932225A (en) * | 2016-06-29 | 2016-09-07 | 中国科学院青岛生物能源与过程研究所 | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery |
| CN106450482A (en) * | 2016-12-09 | 2017-02-22 | 中国电子新能源（武汉）研究院有限责任公司 | Method for manufacturing all-solid soft-packaged lithium ion battery |
| CN107394261B (en) * | 2017-07-03 | 2019-12-20 | 清华大学深圳研究生院 | Inorganic/organic composite film solid electrolyte for lithium metal battery and preparation method thereof |
| CN109473722A (en) * | 2018-09-17 | 2019-03-15 | 浙江极马能源科技股份有限公司 | A method of manufacture circular cylindrical solid battery |
| CN109449482A (en) * | 2018-09-17 | 2019-03-08 | 浙江极马能源科技股份有限公司 | A method of manufacture flexible solid battery |
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| CN109546152A (en) * | 2018-11-13 | 2019-03-29 | 南昌大学 | A kind of solid lithium battery electrode material and preparation method thereof |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
| CN113921822A (en) * | 2021-10-08 | 2022-01-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Flexible self-healing deep sea solid-state battery |
| CN114014383A (en) * | 2021-11-05 | 2022-02-08 | 广东佳纳能源科技有限公司 | High-tap-density positive electrode material and preparation method of positive electrode piece |
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| CN102779983B (en) * | 2012-08-15 | 2014-06-04 | 泉州劲鑫电子有限公司 | Production method for positive pole of high-power nickel-metal hydride battery |
| KR102133786B1 (en) * | 2012-08-28 | 2020-07-14 | 어플라이드 머티어리얼스, 인코포레이티드 | Solid state battery fabrication |
| CN102800865A (en) * | 2012-08-28 | 2012-11-28 | 吴永胜 | Lithium battery with total solid ions for conducting power |
| CN103474620B (en) * | 2013-09-16 | 2016-04-20 | 向勇 | Solid lithium ion electrode, battery and preparation method thereof |
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